Laminated product



inated material in Patented Mar. 23, 1943 2,314,701

UNITED STATES PATENT OFFICE LAMINATED raonuo'r Mortimer T. Harvey, EastOrange, N. .12, assigiior to The Harvel Corporation, a corporation ofNew Jersey No Drawing. Application November 15, 1938,

Serial No. 240,496 2 Claims. (C1. 154-'-43) 'fl'ie present inventionrelates generally to lam-. ton, muslin, duck, canvas and others commonlywhich sheets or strips of 11- used and cloth or fabric woven orotherwise made brous material are bound together by a phenolof asbestosor glass threads. aldehyde type of condensation product and the Thecondensation product used in the practice methods and steps of makingand using said of the present invention are obtained by conlaminatedmaterial. densing a reactive methylene group containing Binders of thephenol-aldehyde type of con-' material and two kinds of phenols, first,a phenol densation product have been used for a long time such ascarbolic acid, the cresols and the xylenols in making laminatedmaterial, but certain dimand second, a phenol having on the nucleusculties and disadvantages in the manufacture thereof an unsaturated openchain hydrocarbon thereof or in the use thereof have appeared andsubstituent such as cashew nut shell liquid, carit is an object of thepresent invention to provide danol, marking nut shell liquid, urushiol,butaa product and methods and steps for making dienyl phenol and paraallyl phenol, all of which and using the product which avoid suchdifllcullatter are or contain phenols of the specified type ties anddisadvantages. having at least two of the readily reactive posi- One ofthe particular objects of the present intions unsubstituted.Condensations reactions of vention is that of providing an intermediatean aldehyde (or reactive methylene group conproduct in which sheets orstrips of fibrous mataining material) with a phenol containing an terialare cemented together by a potentially unsaturated open chainhydrocarbon substituent reactive condensation product which will wet theand having at least two of the readily reactive surfaces of fibrousmaterial sufilciently to cement positions unsubstituted, with or withoutco-conthem together, which potentially reactive condendensation of analdehyde with a phenol such as sation product has sumcient body to holdit from carbolic acid, the cresols and the xylenols, have been known forsome time as disclosed in my flowing from and leaving the surface of andpassing into the pores or interstices of fibrous mate- Patent Numbers1,725,797 of August 2'7, 1929, and rial, particularly when pressure andheat are ap- 1,821,095 of September 1, 1935, and the use of plied, andyet is soluble in a thinner such as cashew nut shell liquid-aldehydecondensation for alcohol, benzol or alcohol or mixtures thereof. makingimpregnated fabrics for use in electrical Another object of the presentinvention is to insulation is described in my Patent 1,725,791 ofprovide a laminated material in which holes or August 2'7, 1929, but thepresent invention brings notches can be punched at a high rate. of speedout improvements for the making of punched at normal temperatures(without heating) withlaminations at a high rate of speed which involvesout delamination. An advantage obtained by the a combination of physicalrequirements which are achievement of this object is that thecondensaobtained by the methods of this invention. tion product can begiven its ultimate or other Formaldehyde is used as a specific examplefor predetermined set or degree. of condensation at illustrativepurposes herein but other reactive the time the laminated material iscured to carry methylene group containing materials such as thepotentially reactive cementitious condensation hexamethylene tetramine,paraformaldehyde, product to a solid state. Another advantage isfurfuraldehyde and others can be used for the that the necessity forheating of the laminated same purpose in certain cases. material toprevent delamination during punch- Examples of aldehyde-mixed phenolscondensation products of the kind involved herein and ing is obviated.

Another advantage of the present invention is the methods and steps formaking them are given that good, clean edges are 1' it at the punchedbelow for the purpose of disclosing how the presholes or notches, freeof threads or shreds. ent invention can be used.

Another object and advantage of the present Example 1.-Eighty-sevenpounds of 92% pheinvention is a laminated material which has high nol(carbolic acid), sixty-eight pounds of comelectrical insulating valuesfor direct current or mercial formaldehyde solution (37.5% solution) foralternating currents of from the low to the and 1330 cubic centimetersof a solution of amextremely high frequencies, known as radio fremoniain water (26, sp. gr. 0.90, 27 to 28% by quencies. weight) are heatedunder a refiux condenser for Examples of the fibrous materials suitablefor about one hour after which eighty pounds of use in the practice ofthe present invention are cashew nut shell liquid (from which thenaturally paper, blotting board, card board and similar sooccurringmetals have been removed by, for excalled boards, cloth or textilefabric such as cot- 55 ample, the method disclosed in Patent Number2,067,919), twenty-one pounds, five ounces of formaldehyde solution(same as above) and four hundred and eighteen cubic cerfiimeters ofammonia solution (same as above) are added and heating under the refluxis continued for onehalf our after which the water is removed at 150 F.under vacuum.

The resin produced by these steps is. soluble, warm or cold, in alcoholor toluol and in other solvents.

For making laminations the resin of Example 1, above, (and of the ,otherexamples hereinafter given) can beapplied by means of a solvent to thesurface of sheets or rolls of paper, cloth or other material and thesolvent driven ofl, for example at about 200 F. to about 225 F., duringwhich heating the resin condenses further to a stag in which it isinsoluble inalcohol but is fusible. The coated material is then built upin layer to th desired thickness and pressed at a temperature of about300 F. to about 350 F., for example, to set or condense the resinfurther to the ultimate or other predetermined degree at which it isinfusible. v

In the followingfurther examples the phenol (carbolic acid), theformaldehyde, th ammonia solution and the cashew nut shell liquid are ofthe specifications set forth in Example 1 above, to which reference ishereby made.

Example 2.'Iwenty-two pounds of carbolic acid, twenty pounds of cardanol(described in Patent Number 2,098,824, to which reference is herebymade), twenty-four pounds of formaldehyde and one-thousand one hundredcubic centimeters of ammonia solutionand heated under the refluxcondenser for about two hours'and I then dehydrated at reduced pressure.,This re'sin is soluble at this stage in alcohol and in toluol and uponfurther heating passes through a stage in which it is insoluble inalcohol (or toluol) but is fusible and then passes to the infusiblestage.

Example 3.'Eighty-seven pounds of phenol (carbolic acid), forty poundsof cardanol, seventy-eight pounds of formaldehyde and fifteen hundredand forty pounds of ammonia solution are heated under the refluxcondenser for about two hours after which forty pounds of cashew nutshell liquid, eleven pounds of formaldehyde and two hundred and tencubic centimeters of ammonia, solution are added and the under refluxcontinued for about a half-hour after which the resin is dehydrated atabout 150 F. under vacuum.

It is to be noted that for the purpose of the present invention in thosecases in which cashew' nut shell liquid is used it is advantageous tostart the aldehyde condensation of the phenol (carbolic acid), and ofthe cardanol when used, before aldehyde condensation of the cashew nutshell liquid is commenced because the latter con-- denses so quicklywith an aldehyde (or other reactive methylene containing material) thatit will go over to a stage in which it is too' heavy or viscous and dificultly soluble before the phenol (or cardan is sufiiciently reactedwith the aldehyde.-

heating fibers therein and can be generally stated that for every moleof speed at normal temperatures such as thickness laminated or the ofthe fibrous material to be closeness or looseness of the to suit otherconditions. It

phenol (carbolic acid), or its equivalent such as one of the cresolsmole to about 0.7 mole of cashew nut shell liquid or cardanol or otherphenol having an unsaturated hydrocarbon substituent can be used, andthat for every mole of a phenol of whatever kind "used from about 0.6mole to about 1.5 moles of formaldehyde (HCHO) or its equivalent can beused.

The laminated invention is suitable for making ele'ctricalinsulatingparts; for making pulleys and gears for machinery; for making abrasivewheels or discs by laminating sheets or discs of cloth, paper or othermaterial carrying abrasive material such.

as sand, carborundum and other granular material or one or both sides ofsurfaces of the solvent sheets or discs; for .example friction elementssuch as brake and clutch linings, for example, with the. use oflaminations of asbestos sheets or plates, with or without othermaterials; and the laminated material of the tion is suitable for use inLaminated stock or to the present invention is resistant to chlorine,alkalis .and "other chemicals and is resistant to moisture. I I

Having thus described my invention, what I claim and desire to protec byLetters Patent is:

1. A laminated product 0 fact that it can be punched the I artsgenerally.

at a high rate of without delamination, comprising essentially sheets ofcellulosic fibrous material bound together by a condensation product offormaldehyde and a mixture of carbolic acid and cardanol, the amount ofsaid formaldehyde reacted being from about 0.6 mole to about 1.5molesfor each mole of the phenols reacted therewith, the ratio of saidcarbolic acid to cardanol in said mixture being about 1 mole to about0.16 mole to 0.7 mole, said condensation product being thermosetting.

2. A laminated product characterized by the fact that it can bepunchedat a high rate of speed at normal temperatures without delamination,comprising essentially sheets of cellulosic fibrous material boundtogether by a condensation product of formaldehyde and a'mixture of acidcashew nut shell liquid and cardanol, the amount of said formaldehydereacted being from about 0.6 mole to about 1.5 moles for each mole ofthe phenols reacted therewith, the ratio of said carbolic acid tocardanol and cashew nut shell liquid in saidmixture being about 1 moleto about 0.16 mole to 0.7 mole, said condensation product beingthermosetting.

, 'MOR'I'IMER 'r. HARVEY.

or the xylenols, from about 0.16

material or stock of the present present inven-' material made accordingaracterized by the

